Open Data supplied by Natural Environment Research Council (NERC)

SPX Bran+Luebbe Autoanalyser 3

The instrument uses continuous flow analysis (CFA) with a continuous stream of material divided by air bubbles into discrete segments in which chemical reactions occur. The continuous stream of liquid samples and reagents are combined and transported in tubing and mixing coils. The tubing passes the samples from one apparatus to the other with each apparatus performing different functions, such as distillation, dialysis, extraction, ion exchange, heating, incubation, and subsequent recording of a signal.

An essential principle of the system is the introduction of air bubbles. The air bubbles segment each sample into discrete packets and act as a barrier between packets to prevent cross contamination as they travel down the length of the tubing. The air bubbles also assist mixing by creating turbulent flow (bolus flow), and provide operators with a quick and easy check of the flow characteristics of the liquid.

Samples and standards are treated in an exactly identical manner as they travel the length of the tubing, eliminating the necessity of a steady state signal, however, since the presence of bubbles create an almost square wave profile, bringing the system to steady state does not significantly decrease throughput and is desirable in that steady state signals (chemical equilibrium) are more accurate and reproducible.

The autoanalyzer can consist of different modules including a sampler, pump, mixing coils, optional sample treatments (dialysis, distillation, heating, etc), a detector, and data generator. Most continuous flow analyzers depend on color reactions using a flow through colorimeter, however other methods have been developed that use ISE, flame photometry, ICAP, fluorometry, and so forth.

World Precision Instruments Liquid Waveguide Capillary Cell

Liquid Waveguide Capillary Cell (LWCC) is a flow cell for absorbance measurements in the ultraviolet, visible and near infra-red ranges. Pathlengths range from 50-500cm, with increasing measurement sensitivity from 50 to 500-fold. The flow cells are fiber coupled and have a very small sample volume ranging from 125µL (50cm pathlength) to 1,250µL (500cm pathlength).

The sample solution is introduced into the LWCC at the liquid input. Light is coupled into the LWCC from a light source via a fiber optic cable. After passing through the LWCC, light is collected with an optical fiber and guided to a detector. The concentration of the sample is determined by measuring its absorbance in the LWCC, similar to a standard UV/VIS spectrometer.

Specifications

Model

LWCC-3050

LWCC-3100

LWCC-3250

LWCC-3500

Optical Pathlength

50cm

100cm

250cm

500cm

Internal Volume

125µL

250µL

625µL

1250µL

Fiber Connection

500um SMA

Transmission @254nm*

20

10

5

-

Transmission @540nm*

35

30

25

20

Noise [mAU]**

<0.1

<0.2

<0.5

<1.0

Maximum Pressure 100 PSI

Wetted Material PEEK, Fused Silica, PTFE

Liquid Input Standard 10-32 Coned Port Fitting

* Referenced using coupled 500µm fibers

** Measured using ASTM E685-93

*** A one-meter waveguide of 550µm internal diameter requires approximately 1.5 psi for water flow of 1.0 mL/min.

Niskin Bottle

The Niskin bottle is a device used by oceanographers to collect subsurface seawater samples. It is a plastic bottle with caps and rubber seals at each end and is deployed with the caps held open, allowing free-flushing of the bottle as it moves through the water column.

Standard Niskin

The standard version of the bottle includes a plastic-coated metal spring or elastic cord running through the interior of the bottle that joins the two caps, and the caps are held open against the spring by plastic lanyards. When the bottle reaches the desired depth the lanyards are released by a pressure-actuated switch, command signal or messenger weight and the caps are forced shut and sealed, trapping the seawater sample.

Lever Action Niskin

The Lever Action Niskin Bottle differs from the standard version, in that the caps are held open during deployment by externally mounted stainless steel springs rather than an internal spring or cord. Lever Action Niskins are recommended for applications where a completely clear sample chamber is critical or for use in deep cold water.

Clean Sampling

A modified version of the standard Niskin bottle has been developed for clean sampling. This is teflon-coated and uses a latex cord to close the caps rather than a metal spring. The clean version of the Levered Action Niskin bottle is also teflon-coated and uses epoxy covered springs in place of the stainless steel springs. These bottles are specifically designed to minimise metal contamination when sampling trace metals.

Deployment

Bottles may be deployed singly clamped to a wire or in groups of up to 48 on a rosette. Standard bottles have a capacity between 1.7 and 30 L, while Lever Action bottles have a capacity between 1.7 and 12 L. Reversing thermometers may be attached to a spring-loaded disk that rotates through 180° on bottle closure.

Originator's Protocol for Data Acquisition and Analysis

Water samples were taken from the Sea-Bird CTD rosette system. The micro-molar samples were collected into acid-clean 60 ml HDPE (nalgene) sample bottles and the nano-molar samples into 120 ml HDPE (nalgene) sample bottles. Analysis for nutrients was completed within 2 hours for mirco-molar and 3 hours for nano-molar measurements in all cases. Clean handling techniques were employed to avoid contamination of the samples. Nano-molar measurements were also made from samples collected underway each day at 15:00 from the ship's non-toxic supply where concentrations were lower than the detectible level from micro-molar analysis on sea-water.

The main nutrient analyser was a 5-channel Bran and Luebbe AAIII segmented flow autoanalyser. The analytical chemical methodologies used were according to Brewer and Riley (1965) for nitrate, Grasshoff (1976) for nitrite, Kirkwood (1989) for phosphate and silicate, and Mantoura and Woodward (1983) for ammonium.

Nanomolar ammonium concentrations were obtained using an adapted method from Jones (1991); this uses a fluorescent analysis technique following ammonia gas diffusion out of the samples, passing across a hydrophobic Teflon membrane due to differential pH chemistry.

Nanomolar nitrate+nitrite, nitrate and phosphate concentrations were obtained on some samples using a 3-channel nanomolar analyser. This method combines sensitive segmented flow colorimetric analytical techniques with a Liquid Waveguide Capillary Cell (LWCC). The nitrate and nitrate systems worked throughout the cruise but due to time constraints the phosphate system was only used in the Southern Gyre region and beyond.

BODC Data Processing Procedures

The micro and nano-molar nutrient data were submitted to BODC in two separate Microsoft Excel files. There was no micro- or nanomolar ammonium data in the files provided to BODC.

Station and sample metadata were checked against information held in the BODC database and obtained from the SeaBird CTD log files, scientific logs and reports. There were some discrepancies. For one cast (cast 105) this was due to an obvious mislabelling of the cast number in the originator's file. Other significant discrepancies in sample depths are listed in a table in the Problem Report section below.

Data from the LWCC systems were submitted in units of nmol l -1 . Nano-molar data were divided by 1000 to convert the units to µmol l -1 for storage in the database. Users should be aware that these LWCC measurements are valid to the fourth decimal place. The data were assigned parameter codes defined in BODC parameter dictionary. Data loaded into BODC's database using established BODC data banking procedures.

Data Quality Report

The dataset has been checked by the data originator - any suspect data values were removed from the data set before submission to BODC.

Measurement precision information from data originators

The detection limits for measurements from the AAIII Bran and Luebbe autoanalyser have are 0.02 µmol l -1 , except the colorimetric ammonium which has a detection limit of 0.08 µmol l -1 . Samples in the database with a flag of "<" had concentrations below the specified detection limits.

At low concentrations, the values obtained by the LWCC are likely to be more accurate than those from the AAIII analyser.

Problem Report

Because of a few remaining uncertainties in matching sample measurements with SeaBird bottle firing depths, users should exert caution when using data from the following CTD cast and depth (records marked with an asterisk are believed to be due to typographical errors in the source files):

The Atlantic Meridional Transect - Phase 2 (2002-2006)

Who was involved in the project?

The Atlantic Meridional Transect Phase 2 was designed by and implemented by a number of UK research centres and universities. The programme was hosted by Plymouth Marine Laboratory in collaboration with the National Oceanography Centre, Southampton. The universities involved were:

University of Liverpool

University of Newcastle

University of Plymouth

University of Southampton

University of East Anglia

What was the project about?

AMT began in 1995, with scientific aims to assess mesoscale to basin scale phytoplankton processes, the functional interpretation of bio-optical signatures and the seasonal, regional and latitudinal variations in mesozooplankton dynamics. In 2002, when the programme restarted, the scientific aims were broadened to address a suite of cross-disciplinary questions concerning ocean plankton ecology and biogeochemistry and the links to atmospheric processes.

The objectives included the determination of:

how the structure, functional properties and trophic status of the major planktonic ecosystems vary in space and time

how physical processes control the rates of nutrient supply to the planktonic ecosystem

how atmosphere-ocean exchange and photo-degradation influence the formation and fate of organic matter

The data were collected with the aim of being distributed for use in the development of models to describe the interactions between the global climate system and ocean biogeochemistry.

When was the project active?

The second phase of funding allowed the project to continue for the period 2002 to 2006 and consisted of six research cruises. The first phase of the AMT programme ran from 1995 to 2000.

Brief summary of the project fieldwork/data

The fieldwork on the first three cruises was carried out along transects from the UK to the Falkland Islands in September and from the Falkland Islands to the UK in April. The last three cruises followed a cruise track between the UK and South Africa, only deviating from the traditional transect in the southern hemisphere. During this phase the research cruises sampled further into the centre of the North and South Atlantic Ocean and also along the north-west coast of Africa where upwelled nutrient rich water is known to provide a significant source of climatically important gases.

Please note: the supplied parameters may not have been sampled from all the bottle firings described in the table above. Cross-match the Sample Reference Number above against the SAMPRFNM value in the data file to identify the relevant metadata.